The article contains sections titled: 1. Introduction 2. Uses and Biological Activity 2.1. Therapeutic Uses 2.2. Biological Activity 2.3. Other Uses 3. Syntheses and Reactions 3.1. Ring Syntheses 3.2. N‐Substituted Phenothiazines 3.3. C‐Substituted Phenothiazines 3.4. Analogues and Miscellaneous Compounds 3.5. Other Chemical Properties of the Phenothiazine Nucleus 4. Physical Properties 5. Toxicology
Abstract-In a system where a rigid or frozen conformation constrains an allylic proton to orient nearly perpendicular to the plane of the olefinic bond, the allylic spin coupling may become comparable to, or greater than, the vicinal spin coupling. This anomalous situation is demonstrated in three series of compounds: the adducts of diazoalkanes to 1,2-diazepines, Cpiperidinocyclcalk-2-en-1 -one oximes and heterobicyclo [3,2,0]hept-3,6-dienes, where the NMR spectra have been well established by decoupling experiments.SPIN-spin coupling in NMR spectroscopy is one of the most descriptive physico-chemical phenomena, which allows structural chemists to conceive the shape of a molecule. The relation of the magnitude of the coupling constant with respect to the dihedral angle, as defined by the two hydrogen nuclei under consideration, has developed along a dual approach by empirical correlation as well as by theoretical calculations.2 The applications of these results to the determination of the configuration and of the conformation of a molecule have been widely practised by organic chemists. The early theoretical predictions, based on valence bond calculations, and molecular orbital interaction^,^ culminated in the emergence of the well known Karplus rule: which defines the dependence of coupling constants through 3-and 4-bonds on the dihedral angle, among other factors such as electronegativities of substituents, hybridisation of carbon atoms, and bond angles and lengths, etc. The Karplus rule has undergone various theoretical since its inception and the validity of the rule is convincingly confirmed by the experimental data2 in various types of organic molecules.Garbish4 has estimated 3-and 4-bond vinylic-allylic couplings by considering (r and rr-bond contributions to both types of coupling as a function of the allylic proton conformation. According to this empirical relation, for the 3-(JI2) and 4-bond coupling (113) constants relative to the dihedral angle (see the stereorelationship A), the following set of equations is obtained.From the theory, the term of cos2+ represents the (rbond contribution and the term of sin2+ the rr-bond contribution. Experimentally it is known that a12 is far larger than ~1 3 , since an interaction through four o-bonds is noticeable only in a W-plan (+ = 0"). It is also logical to expect that the term of sin24 becomes important at 4 = 90" where the rr-orbital and the allylic C-H, bond are held parallel, at which configuration (or conformation) the overlap between the orbitals * Professeur associt of CUHR 1971 to 1972; on leave of absence froin Simon Fraser University, Burnaby 2, B.C., Canada.is the best. Although the signs of the coupling constants are opposite in the vicinity of 4 = go", the experimentally observable coupling constants J12 and J13 are determined by the numerical value of b,, and b13. Depending on the factors such as electronegativities of substituents and bond lengths and angles, etc., a situation may arise in which the numerical value of b13 is bigger than b,, in t...
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
customersupport@researchsolutions.com
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.